CN110650991B - Method for producing fluorine-containing ether compound, and fluorine-containing ether compound - Google Patents
Method for producing fluorine-containing ether compound, and fluorine-containing ether compound Download PDFInfo
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- CN110650991B CN110650991B CN201880033220.0A CN201880033220A CN110650991B CN 110650991 B CN110650991 B CN 110650991B CN 201880033220 A CN201880033220 A CN 201880033220A CN 110650991 B CN110650991 B CN 110650991B
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 79
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011737 fluorine Substances 0.000 title claims abstract description 77
- -1 ether compound Chemical class 0.000 title claims abstract description 75
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 332
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims abstract description 20
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000012756 surface treatment agent Substances 0.000 abstract description 35
- 125000000962 organic group Chemical group 0.000 abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 76
- 125000002947 alkylene group Chemical group 0.000 description 69
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 26
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 25
- 239000002904 solvent Substances 0.000 description 25
- 239000002344 surface layer Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000000543 intermediate Substances 0.000 description 13
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 13
- 239000005871 repellent Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920001296 polysiloxane Chemical group 0.000 description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 10
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- WYROLENTHWJFLR-ACLDMZEESA-N queuine Chemical compound C1=2C(=O)NC(N)=NC=2NC=C1CN[C@H]1C=C[C@H](O)[C@@H]1O WYROLENTHWJFLR-ACLDMZEESA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
- C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/63—Halogen-containing esters of saturated acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
- C08G65/3233—Molecular halogen
- C08G65/3236—Fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Disclosed is a method for producing a fluorine-containing ether compound, which enables to produce a fluorine-containing ether compound in high yield, which is useful as an intermediate for a fluorine-containing ether compound that is suitably used as a surface treatment agent. A process for producing a fluorine-containing ether compound, which comprises reacting R 1 OH is reacted with a compound represented by the following formula (1) to obtain a mixture comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3), HO (O) C-R f2 O‑(R f1 O) m ‑R f2 ‑C(O)OH…(1)HO(O)C‑R f2 O‑(R f1 O) m ‑R f2 ‑C(O)OR 1 …(2)R 1 O(O)C‑R f2 O‑(R f1 O) m ‑R f2 ‑C(O)OR 1 8230in (3) wherein R f1 And R f2 Each independently is a perfluoroalkylene group, m is an integer of 2 to 200, (R) f1 O) m Can be composed of more than 2 kinds of R f1 O is formed of R 1 Is a 1-valent organic group.
Description
Technical Field
The present invention relates to a method for producing a fluorinated ether compound and a fluorinated ether compound.
Background
The fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain is suitably used as a surface treatment agent because it can form a surface layer exhibiting high lubricity, water repellency, oil repellency, and the like on the surface of a substrate. A surface treatment agent containing a fluorine-containing ether compound is used, for example, as a surface treatment agent for a member constituting a finger contact surface of a touch panel in applications requiring the performance (rubbing resistance) of maintaining the water/oil repellency of a surface layer not to be lowered even when the surface layer is repeatedly rubbed with a finger and the performance (fingerprint stain removal performance) of easily removing a fingerprint adhering to the surface layer by wiping.
As a fluorine-containing ether compound capable of forming a surface layer excellent in abrasion resistance and fingerprint stain removability on the surface of a base material, a fluorine-containing ether compound having a hydrolyzable silyl group introduced at one end has been proposed (patent document 1). As an intermediate of the fluorine-containing ether compound having a hydrolyzable silyl group introduced at one end, a fluorine-containing ether compound having a hydroxyl group, a carbonyl group-containing group (such as a carboxylic acid halide group or an ester group) at one end is useful. The fluorine-containing ether compound having a hydroxyl group at one end can be produced, for example, as follows (patent document 1).
A compound represented by the following formula (1 b) is fluorinated with a fluorine gas to obtain a mixture composed of a compound represented by the following formula (1 a), a compound represented by the following formula (1 b), and a compound represented by the following formula (1 c).
CF 3 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 C(O)OH…(1a)
HO(O)CCF 2 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 C(O)OH…(1b)
CF 3 (OC 2 F 4 ) p (OCF 2 ) q OCF 3 …(1c)
p and q are, for example, p/q =0.9, p + q ≈ 45.
The mixture is purified using an ion exchange resin to increase the proportion of the compound represented by formula (1 a). The purified mixture is reduced by hydrogenation using a reducing agent to obtain a mixture containing a compound represented by the following formula (2 a) at a high concentration.
CF 3 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 CH 2 OH…(2a)
Further, a method of purifying a mixture composed of a compound represented by formula (1 a), a compound represented by formula (1 b), and a compound represented by formula (1 c) by silica gel chromatography using carbon dioxide in a supercritical state or a subcritical state as fluidity to obtain a mixture containing the compound represented by formula (1 a) at a high concentration has been proposed (patent document 2).
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2012-072272
Patent document 2: japanese patent laid-open No. 2015-164906
Disclosure of Invention
Technical problems to be solved by the invention
However, in the method of fluorinating the compound represented by the formula (1 b) with fluorine gas described in patent document 1, the compound represented by the formula (1 c) is inevitably produced. The compound represented by formula (1 c) is not suitable for a surface treatment agent because it does not have a functional group that interacts with or chemically binds to a substrate. The compound represented by the formula (1 c) is a stable compound, and only the terminal thereof is decomposed, and cannot be reused as a raw material, that is, the compound represented by the formula (1 b). Therefore, the method described in patent document 1 cannot obtain the compound represented by formula (1 a) and the compound represented by formula (2 a) in high yields, which are useful as intermediates of fluorine-containing ether compounds suitably used for surface treatment agents.
An object of the present invention is to provide a process for producing a fluorine-containing ether compound, which can produce a fluorine-containing ether compound in high yield, which is useful as an intermediate for a fluorine-containing ether compound suitable for a surface treatment agent, and a fluorine-containing ether compound, which is useful as an intermediate for a fluorine-containing ether compound suitable for a surface treatment agent.
Technical scheme for solving technical problems
The present invention provides a method for producing a fluorine-containing ether compound having the following configurations [1] to [15], and a fluorine-containing ether compound.
[1]A process for producing a fluorine-containing ether compound, characterized in that R is 1 OH is reacted with a compound represented by the following formula (1) to obtain a mixture containing a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(2)
R 1 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(3)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the component (A) is selected from,
R 1 is a 1-valent organic group.
[2]Such as [1]]The production process described above, wherein the compound represented by the formula (1) is recovered as an unreacted compound represented by the formula (1) and the R 1 The compound represented by the formula (1) in the OH reaction is reused.
[3]Such as [1]]Or [ 2]]The production process described in the above, wherein the compound represented by the formula (3) is recovered and hydrolyzed to obtain the compound represented by the formula (1), and the compound represented by the formula (1) and the R are used as the compound represented by the formula (1) 1 The compound represented by the formula (1) in the OH reaction is reused.
[4] A process for producing a fluorine-containing ether compound, characterized by fluorinating a compound represented by the following formula (2) with a fluorine gas to obtain a compound represented by the following formula (4),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(2)
F-R f2 O-(R f1 O) m -R f2 -C(O)OR f3 …(4)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the component (A) is selected from,
R 1 is an organic group having a valence of 1,
R f3 is derived from R 1 A perfluoroorganic group having a valence of 1.
[5]A process for producing a fluorine-containing ether compound, characterized by reacting a compound represented by the following formula (4) with R 2 Performing ester exchange on OH to obtain a compound shown as a following formula (5),
F-R f2 O-(R f1 O) m -R f2 -C(O)OR f3 …(4)
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R f3 is a perfluorinated organic group having a valence of 1,
R 2 is a 1-valent organic group.
[6] A process for producing a fluorine-containing ether compound, characterized by hydrogenating and reducing a compound represented by the following formula (5) with a reducing agent to obtain a compound represented by the following formula (6),
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
wherein,
R f1 and R f2 Are respectively provided withIndependently of one another is a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 2 is a 1-valent organic group.
[7] A fluorine-containing ether compound represented by the following formula (2) or a fluorine-containing ether compound represented by the following formula (4),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(2)
F-R f2 O-(R f1 O) m -R f2 -C(O)OR f3 …(4)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 1 is an organic group having a valence of 1,
R f3 is a 1-valent perfluoroorganic group.
[8] A process for producing a fluorine-containing ether compound, characterized by reacting a compound represented by the following formula (6) with a compound represented by the following formula (1) to obtain a mixture comprising the compound represented by the following formula (1), a compound represented by the following formula (12) and a compound represented by the following formula (13),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(12)
F-R f2 O-(R f1 O) m -R f2 -CH 2 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(13)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 And O.
[9] The production process according to [8], wherein an unreacted compound represented by the formula (1) is recovered and reused as the compound represented by the formula (1) in the reaction of the compound represented by the formula (1) with the compound represented by the formula (6).
[10] The production process according to [8] or [9], wherein the compound represented by the formula (13) is recovered, hydrolyzed to obtain the compound represented by the formula (1) and the compound represented by the formula (6), and reused as the compound represented by the formula (1) and the compound represented by the formula (6) in the reaction of the compound represented by the formula (1) and the compound represented by the formula (6).
[11] A process for producing a fluorine-containing ether compound, characterized by fluorinating a compound represented by the following formula (12) with fluorine gas to obtain a compound represented by the following formula (14),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(12)
F-R f2 O-(R f1 O) m -R f2 -C(O)OCF 2 -R f2 -(OR f1 ) m -OR f2 -F…(14)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 And O.
[12]A process for producing a fluorine-containing ether compound, characterized in thatReacting a compound represented by the following formula (14) with R 2 Performing ester exchange on OH to obtain a compound shown as a following formula (5),
F-R f2 O-(R f1 O) m -R f2 -C(O)OCF 2 -R f2 -(OR f1 ) m -OR f2 -F…(14)
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 2 is a 1-valent organic group.
[13] A process for producing a fluorine-containing ether compound, characterized by hydrogenating and reducing a compound represented by the following formula (5) obtained by the above production process of [12] with a reducing agent to obtain a compound represented by the following formula (6),
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 2 is a 1-valent organic group.
[14] A process for producing a fluorine-containing ether compound, characterized by reacting a compound represented by the above formula (6) obtained by the above process for producing [13] with a compound represented by the following formula (1) to obtain a mixture comprising a compound represented by the following formula (1), a compound represented by the following formula (12) and a compound represented by the following formula (13),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(12)
F-R f2 O-(R f1 O) m -R f2 -CH 2 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(13)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 And O.
[15] A fluorine-containing ether compound represented by the following formula (12) or a fluorine-containing ether compound represented by the following formula (14),
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(12)
F-R f2 O-(R f1 O) m -R f2 -C(O)OCF 2 -R f2 -(OR f1 ) m -OR f2 -F…(14)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 And O.
Effects of the invention
According to the process for producing a fluorinated ether compound of the present invention, a fluorinated ether compound useful as an intermediate for a fluorinated ether compound suitable for a surface treatment agent can be produced in a high yield.
The fluorine-containing ether compound of the present invention is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
Detailed Description
In the present specification, the compound represented by formula (1) will be referred to as compound (1). The same applies to compounds represented by other formulae.
The following terms in the present specification have the following meanings.
"perfluoroorganic group" refers to a group in which all hydrogen atoms bonded to carbon atoms of an organic group are replaced by fluorine atoms.
The chemical formula of oxyperfluoroalkylene is shown in such a manner that the oxygen atom is located on the right side of the perfluoroalkylene group.
"etheric oxygen atom" means an oxygen atom forming an ether bond (-O-) between carbon atoms.
"hydrolyzable silyl group" refers to a group capable of forming a silanol group (Si-OH) by a hydrolysis reaction. For example, siR in formulas (21) to (24) 3 n L 3-n 。
The "surface layer" refers to a layer formed on the surface of the substrate.
The "number average molecular weight" of the fluorine-containing ether compound was calculated by the following method using NMR analysis.
By using 1 H-NMR and 19 F-NMR was carried out by obtaining the number (average value) of oxyperfluoroalkylene groups based on the terminal groups to calculate the number average molecular weight. The terminal group is, for example, F-R in the formulae (21) to (24) f2 Or SiR 3 n L 3-n 。
[ first Synthesis route of Compound (6) ]
The synthetic route of the compound (6) using the compound (1) as a starting material may, for example, be the first synthetic route described below.
[ solution 1]
(Compound (1))
Compound (1) is the starting material in the synthetic route to compound (6).
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
Wherein R is f1 And R f2 Each independently is a perfluoroalkylene group, m is an integer of 2 to 200, (R) f1 O) m Can be composed of more than 2 kinds of R f1 And O.
<(R f1 O) m >
R is more excellent in the abrasion resistance and fingerprint stain removability of the surface layer comprising the finally obtained surfactant f1 The number of carbon atoms of (b) is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 2, from the viewpoint of more excellent lubricity of the surface layer.
R f1 The structure may be a linear structure or a branched structure, and the linear structure is preferable from the viewpoint of more excellent friction resistance and lubricity of the surface layer.
The compound (1) has (R) f1 O) m Therefore, the content of fluorine atoms is large. Therefore, the finally obtained surface treatment agent can form a surface layer excellent in water repellency and oil repellency, abrasion resistance, and fingerprint stain removability.
m is preferably an integer of 5 to 150, particularly preferably an integer of 10 to 100. When m is not less than the lower limit of the above range, the surface layer comprising the finally obtained surface treatment agent is excellent in water and oil repellency. When m is equal to or less than the upper limit of the above range, the surface layer is excellent in friction resistance. That is, if the number average molecular weight of the surface treatment agent is too large, the number of hydrolyzable silyl groups present per unit molecular weight decreases, and the abrasion resistance of the surface layer decreases.
In (R) f1 O) m In which more than 2 kinds of R exist f1 In the case of O, each R f1 The bonding order of O is not limited, and may be random, alternate, or block arrangement.
There are more than 2 kinds of R f1 O means that 2 or more R having different carbon atoms are present f1 O, and the presence or absence of a side chain having the same number of carbon atoms or the type (side chain) of the side chainNumber of chains and number of carbons of side chain, etc.) of 2 or more kinds of R f1 O。
With respect to 2 or more kinds of R f1 Configuration of O, for example, in the case of the fluorine-containing ether compound of the example, { (CF) 2 O) x1 (CF 2 CF 2 O) x2 The structures shown represent x1 (CF) 2 O) and x2 (CF) 2 CF 2 O) are randomly configured. Furthermore, (CF) 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) x3 The structure shown represents x3 (CF) 2 CF 2 O) and x3 (CF) 2 CF 2 CF 2 CF 2 O) are alternately arranged.
As (R) f1 O) m From the viewpoint of further improving the abrasion resistance, fingerprint stain removability and lubricity of the surface layer comprising the finally obtained surface treatment agent, { (CF) is preferred 2 O) m1 (CF 2 CF 2 O) m2 }、(CF 2 CF 2 O) m3 、(CF 2 CF 2 CF 2 O) m4 、(CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) m5 And 1 to 4 other (R) s at one or both ends thereof f1 O) group. Having 1 to 4 other groups (R) at one or both ends thereof f1 O) group, for example, (CF) 2 CF 2 O) 2 {(CF 2 O) m1 (CF 2 CF 2 O) m2-2 }、(CF 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) m5-1 (CF 2 CF 2 O), and the like. As (R) f1 O) m Particularly preferably has { (CF) 2 O) m1 (CF 2 CF 2 O) m2 The group of (a).
Wherein m1 is an integer of 1 or more, m2 is an integer of 1 or more, m1+ m2 is an integer of 2 to 200, and m1 CF 2 CF of O and m2 2 CF 2 The order of bonding of O is not limited. m3 and m4 are each an integer of 2 to 200, and m5 is an integer of 1 to 100.
<R f2 Radical (I)>
R is more excellent in the abrasion resistance and fingerprint stain removability of the surface layer comprising the finally obtained surfactant f2 The number of carbon atoms of (b) is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 2, from the viewpoint of more excellent lubricity of the surface layer.
For example, in (R) f1 O) m Is { (CF) 2 O) m1 (CF 2 CF 2 O) m2 And (CF) 2 CF 2 O) m3 In the case of (1), R f2 Has a carbon number of 1 in (R) f1 O) m Is (CF) 2 CF 2 CF 2 O) m4 In the case of (1), R f2 Has a carbon number of 2 in (R) f1 O) m Is (CF) 2 CF 2 O-CF 2 CF 2 CF 2 CF 2 O) m5 In the case of (2), R f2 Is 3 carbon atoms and is a straight chain. In addition, in R f1 In the case of perfluoroalkylene having a branch, R f2 Sometimes perfluoroalkylene with a branch, for example as in R f1 Is (CF) 3 )CF 2 O) in the case of R f2 Is CF (CF) 3 )。
If R is f2 The surface layer is linear, and therefore, excellent in friction resistance and lubricity.
Examples of commercially available products of the compound (1) include FOMBLIN (registered trademark) ZDIC 4000 manufactured by SUVISUITAKS corporation (\125771252312505\1247712424631241247112473.
(Process for producing Compound (2))
The compound (2) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
In the first embodiment of the process for producing a fluorinated ether compound of the present invention, R is 1 A method in which OH is reacted with the compound (1) to obtain a mixture comprising the compound (1), the compound (2) and the compound (3).
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(2)
R 1 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(3)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same. R 1 Is a 1-valent organic group.
As R 1 Examples of the "hydrocarbyl" may include substituted 1-valent hydrocarbon groups. Examples of the hydrocarbyl group having a valence of 1 include an alkyl group, an aryl group and a cycloalkyl group. R 1 The carbon number of (2) is preferably 1 to 20, particularly preferably 1 to 10.
R 1 The carboxyl group is fluorinated simultaneously with the reaction with fluorine gas, but it is desirable that the reaction other than the substitution of the hydrogen atom with a fluorine atom does not occur. In this respect, R 1 May contain an etheric oxygen atom, preferably a 1-valent hydrocarbon group in which a part of hydrogen atoms may be substituted with fluorine atoms. In addition, R is from the viewpoint of facilitating the reaction in the esterification reaction after fluorination 1 OH is preferably a primary alcohol.
As R 1 Preferably an alkyl group, derived from R which can be easily removed as a by-product formed in the esterification reaction after fluorination 1 An alkyl group having 1 to 10 carbon atoms is particularly preferable from the viewpoint of the OH compound (having a low boiling point).
Compound (1) and R 1 The reaction conditions for OH are not particularly limited as long as they are reaction conditions for ordinary esterification.
As a method for recovering each compound from the mixture, a known purification method (column chromatography using silica gel or an ion exchange resin, or the like) may be mentioned.
The recovered compound (2) is used for the production of the next compound (4).
The recovered compound (1) is preferable as the compound (1) and R 1 The compound (1) in the OH reaction is reused.
The recovered compound (3) is preferably hydrolyzed to obtain compound (1), which is used as compound (1) and R 1 The compound (1) in the OH reaction is reused.
Since the compound (1) and the compound (3) can be reused as raw materials, the compound (1) and the compound (3) are not wasted. Therefore, the compound (2) and the compound (4), the compound (5) and the compound (6) can be produced in high yield.
(Process for producing Compound (4))
The compound (4) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
The second embodiment of the process for producing a fluorine-containing ether compound of the present invention is a process for obtaining a compound (4) by fluorinating a compound (2) with a fluorine gas.
F-R f2 O-(R f1 O) m -R f2 -C(O)OR f3 …(4)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same. R f3 Is derived from R 1 A perfluoroorganic group having a valence of 1.
R f3 Is the reaction product of R of the compound (2) 1 Fluorinated group, therefore as R f3 Examples of the "R" may include 1 Fluorinated radical, preferably R 1 The preferred embodiment of (1) is a group obtained by fluorination.
The reaction conditions for fluorinating the compound (2) with fluorine gas are not particularly limited as long as they are normal fluorination reaction conditions.
(Process for producing Compound (5))
The compound (5) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
In a third embodiment of the process for producing a fluorinated ether compound of the present invention, the compound (4) and R are 2 A method for obtaining the compound (5) by transesterification of OH.
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same. R 2 Is a 1-valent organic group.
As R 2 Examples of the "hydrocarbyl" may include substituted 1-valent hydrocarbon groups. Examples of the hydrocarbyl group having a valence of 1 include an alkyl group, an aryl group and a cycloalkyl group. R is 1 The carbon number of (2) is preferably 1 to 20, particularly preferably 1 to 10.
As R 2 Preferably alkyl, from R 2 OH has a low boiling point and R is easily removed in a subsequent step 2 From the viewpoint of OH, an alkyl group having 1 to 10 carbon atoms is particularly preferable.
Compound (4) and R 2 The reaction conditions for OH are not particularly limited as long as they are reaction conditions for general transesterification.
(Process for producing Compound (6))
The compound (6) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
In the method for producing a fluorine-containing ether compound of the present invention, the compound (6) can be obtained by hydrogenation reduction of the compound (5) with a reducing agent.
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same.
Examples of the reducing agent include hydrogen gas in the presence of sodium borohydride, lithium aluminum hydride, borane (monoborane, diborane, etc.), a metal catalyst (palladium catalyst, platinum catalyst, etc.), and the like.
The reaction conditions of the compound (5) and the reducing agent are not particularly limited as long as they are reaction conditions for ordinary hydrogenation reduction.
[ second Synthesis route of Compound (6) ]
As another synthetic route of the compound (6) using the compound (1) as a starting material, the following second synthetic route can be exemplified.
[ solution 2]
(Process for producing Compound (12))
The compound (12) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
The fourth embodiment of the process for producing a fluorine-containing ether compound of the present invention is a process for obtaining a mixture containing compound (1), compound (12) and compound (13) by reacting compound (6) with compound (1).
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(12)
F-R f2 O-(R f1 O) m -R f2 -CH 2 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OCH 2 -R f2 -(OR f1 ) m -OR f2 -F…(13)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same.
(R) of Compound (1) f1 O) m With (R) of Compound (6) f1 O) m May be the same or different. From the viewpoint of obtaining a uniform compound as the compound (5) obtained from the following compound (14) and the compound (6) obtained from the compound (5), it is preferable that (R) of the compound (1) f1 O) m With (R) of Compound (6) f1 O) m Are the same.
The reaction conditions of the compound (1) and the compound (6) are not particularly limited as long as they are reaction conditions for ordinary esterification.
As a method for recovering each compound from the mixture, a known purification method (column chromatography using silica gel or an ion exchange resin, or the like) may be mentioned.
The recovered compound (12) is used for the production of the next compound (14).
The recovered compound (1) is preferably reused as the compound (1) in the reaction of the compound (1) and the compound (6).
The recovered compound (13) is preferably hydrolyzed to obtain compound (1) and compound (6), and reused as compound (1) and compound (6) in the reaction of compound (1) and compound (6).
By reusing the compound (1) and the compound (13) as raw materials, the compound (12), the compound (14), the compound (5), and the compound (6) can be produced in high yield.
(method for producing Compound (14))
The compound (14) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
The fifth embodiment of the process for producing a fluorine-containing ether compound of the present invention is a process for obtaining a compound (14) by fluorinating a compound (12) with a fluorine gas.
F-R f2 O-(R f1 O) m -R f2 -C(O)OCF 2 -R f2 -(OR f1 ) m -OR f2 -F…(14)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same.
The reaction conditions for fluorinating the compound (12) with fluorine gas are not particularly limited as long as they are normal fluorination reaction conditions.
(Process for producing Compound (5))
The compound (5) is useful as an intermediate of a fluorine-containing ether compound suitable for a surface treatment agent.
In a sixth embodiment of the process for producing a fluorinated ether compound of the present invention, R is 2 A method for reacting OH with the compound (14) to obtain the compound (5).
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same. R 2 Also with R as described above 2 R in OH 2 Similarly, the preferred embodiments are also the same.
Compounds (14) and R shown in the following formula 2 The reaction mechanism of OH. 2 moles of R 2 OH was reacted with 1 mol of compound (14) to produce 2 mol of compound (5).
[ solution 3]
Compound (14) and R 2 The reaction conditions for OH are not particularly limited as long as they are reaction conditions for general transesterification.
(Process for producing Compound (6))
In the method for producing a fluorinated ether compound of the present invention, compound (6) can be obtained by hydrogenation reduction of compound (5) obtained from compound (14) in the same manner as in the above-described method.
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same.
It is preferable to reuse a part of the obtained compound (6) as an alcohol to be reacted with the compound (1) as a starting material.
As the alcohol to be reacted with the compound (1), R other than the compound (6) is used 1 In the case of OH, it is wasted in passing through the compound (4) and R in the production of the compound (5) 2 R formed by transesterification of OH f3 OH (derived from R) 1 Alcohols of OH). On the other hand, as the alcohol to be reacted with the compound (1), a compound is usedIn the case of the product (6), 2 moles of the compound (5) are produced from 1 mole of the compound (14) at the time of producing the compound (5), and the alcohol (compound (6)) used initially is not wasted.
[ surface treating agent ]
Examples of the fluorine-containing ether compound which can be produced using the compound (6) as a raw material and is suitably used for the surface treatment agent include a compound (21), a compound (22), a compound (23), and a compound (24).
F-R f2 O-(R f1 O) m -R f2 -CH 2 O-Q 1 -SiR 3 n L 3-n …(21)
F-R f2 O-(R f1 O) m -R f2 -CH 2 -(X) r -Q 2 -N[-Q 3 -SiR 3 n L 3-n ] 2 …(22)
F-R f2 O-(R f1 O) m -R f2 -CH 2 O-Q 4 -(O) s -C[-(O) t -Q 5 -SiR 3 n L 3-n ] 3 …(23)
F-R f2 O-(R f1 O) m -R f2 -CH 2 O-Q 6 -Si[-Q 7 -SiR 3 n L 3-n ] 3 …(24)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same. Wherein R is 3 Is a hydrogen atom or a 1-valent hydrocarbon group, L is a hydrolyzable group, and n is an integer of 0 to 2.
In the formula (21), Q 1 Is a group of alkylene or an organopolysiloxane residue having an etheric oxygen atom or a valence of 2 between carbon-carbon atoms of the alkylene group having 2 or more carbon atoms.
In the formula (22), X is an etheric oxygen atom or-NH-, Q 2 Is a single bond, alkylene, or a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of alkylene having 2 or more carbon atoms, and r is 0 or 1 (wherein, in Q 2 R is 0 when it is a single bond), Q 3 Is alkyleneOr a group having an etheric oxygen atom, -NH-or a 2-valent organopolysiloxane residue between carbon-carbon atoms of an alkylene group having 2 or more carbon atoms, 2 [ -Q ] 3 -SiR 3 n L 3-n ]May be the same or different.
In the formula (23), Q 4 Is a single bond, alkylene or a group having an etheric oxygen atom between carbon-carbon atoms of alkylene having 2 or more carbon atoms, Q 5 Is alkylene or a group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon-carbon atoms of alkylene having 2 or more carbon atoms, and s is 0 or 1 (wherein Q is 4 S is 0 when it is a single bond), t is 0 or 1,3 [ - (O) t -Q 5 -SiR 3 n L 3-n ]May be the same or different.
In the formula (24), Q 6 Is alkylene or a group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon-carbon atoms of alkylene having 2 or more carbon atoms, Q 7 Is alkylene or a group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon-carbon atoms of alkylene having 2 or more carbon atoms, and has 3 [ -Q ] 7 -SiR 3 n L 3-n ]May be the same or different.
Examples of the fluorine-containing ether compound which can be produced using the compound (5) as a raw material and is suitably used for the surface treatment agent include a compound (25), a compound (26), a compound (27), and a compound (28).
F-R f2 O-(R f1 O) m -R f2 -C(O)N(R 5 )-Q 8 -SiR 3 n L 3-n …(25)
F-R f2 O-(R f1 O) m -R f2 -C(O)N(R 6 )-Q 9 -(O) u -C[-(O) v -Q 10 -SiR 3 n L 3-n ] 3 …(26)
F-R f2 O-(R f1 O) m -R f2 -C[-O-Q 11 -SiR 3 n L 3-n ][-Q 12 -SiR 3 n L 3-n ] 2 …(27)
F-R f2 O-(R f1 O) m -R f2 -C(OH)[-Q 13 -SiR 3 n L 3-n ] 2 …(28)
Wherein (R) f1 O) m And R f2 With (R) specified in the Compound (1) f1 O) m And R f2 Similarly, the preferred embodiments are also the same. R 3 L and n with R specified in the Compound (21) etc 3 L and n are the same.
In the formula (25), R 5 Is a hydrogen atom or an alkyl group, Q 8 Is a group of alkylene or an organopolysiloxane residue having an etheric oxygen atom or a valence of 2 between carbon-carbon atoms of the alkylene group having 2 or more carbon atoms.
In the formula (26), R 6 Is a hydrogen atom or an alkyl group, Q 9 Is a single bond, alkylene or a group having an etheric oxygen atom between carbon-carbon atoms of alkylene having 2 or more carbon atoms, Q 10 Is alkylene or a group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon-carbon atoms of alkylene having 2 or more carbon atoms, and u is 0 or 1 (wherein Q is 9 U is 0 when it is a single bond), v is 0 or 1,3 [ - (O) v -Q 10 -SiR 3 n L 3-n ]May be the same or different.
In the formula (27), Q 11 Is alkylene, a group having an etheric oxygen atom or a silylene skeleton between carbon-carbon atoms of the alkylene group having 2 or more carbon atoms, or a group having a 2-valent organopolysiloxane residue or dialkylsilylene group at the end of the carbon-carbon atom or the side bonded to O of the alkylene group having 2 or more carbon atoms, Q 12 Is alkylene or alkylene having 2 or more carbon atoms and 2Q 12 Which may be the same or different, 3-SiRs 3 n L 3-n May be the same or different.
In formula (28), Q 13 Is alkylene or a group having an etheric oxygen atom or a 2-valent organopolysiloxane residue between carbon-carbon atoms of alkylene having 2 or more carbon atoms, 2 [ -Q ] 13 -SiR n L 3-n ]May be different groups.
(F-R f2 Base)
Since it has F-R at the end f2 Therefore, one side of the surface treating agent is terminated with CF 3 The other terminal is a hydrolyzable silyl group. The surface treatment agent having such a structure can form a surface layer having a low surface energy, and therefore, the surface layer is excellent in lubricity and friction resistance. On the other hand, in the case of conventional fluorine-containing ether compounds having hydrolyzable silyl groups at both ends, lubricity and abrasion resistance of the surface layer are insufficient.
(Q 1 base-Q 13 Base)
As Q 1 The alkylene group having 1 to 10 carbon atoms or the alkylene group having 2 to 10 carbon atoms has an etheric oxygen atom between carbon-carbon atoms, and the alkylene group having 1 to 7 carbon atoms or the alkylene group having 2 to 7 carbon atoms has an etheric oxygen atom between carbon-carbon atoms. From the viewpoint of ease of production of the compound (21), -CH is preferred 2 CH 2 CH 2 -or-CH 2 CH 2 OCH 2 CH 2 CH 2 - (where the right side is bonded to Si).
As Q 2 The alkylene group having 1 to 10 carbon atoms is preferably a single bond, or a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms, and particularly preferably a single bond, an alkylene group having 1 to 7 carbon atoms, or a group having an etheric oxygen atom or-NH-between carbon-carbon atoms of the alkylene group having 2 to 7 carbon atoms. As (X) r Q 2 From the viewpoint of ease of production of the compound (22), a single bond, -OCH are preferred 2 CH 2 -or-NHCH 2 CH 2 - (where the right side binds to N).
As Q 3 The alkylene group having 1 to 10 carbon atoms or the group having an etheric oxygen atom or-NH-between carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms is preferable, and the alkylene group having 1 to 7 carbon atoms or the group having an etheric oxygen atom or-NH-between carbon-carbon atoms of the alkylene group having 2 to 7 carbon atoms is particularly preferable. From the viewpoint of ease of production of the compound (22), -CH is preferred 2 CH 2 CH 2 -or-CH 2 CH 2 OCH 2 CH 2 CH 2 - (where the right side is bonded to Si).
As Q 4 The carbon atom-containing alkylene group is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 10 carbon atoms, and particularly preferably a single bond, an alkylene group having 1 to 7 carbon atoms, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 7 carbon atoms. As Q 4 -(O) s From the viewpoint of ease of production of the compound (23), a single bond, -CH is preferred 2 -、-CH 2 CH 2 O-or-CH 2 CH 2 OCH 2 - (where the right side is bound to C).
As Q 5 The alkylene group having 1 to 10 carbon atoms or the alkylene group having 2 to 10 carbon atoms has an etheric oxygen atom between carbon-carbon atoms, and the alkylene group having 1 to 7 carbon atoms or the alkylene group having 1 to 7 carbon atoms has an etheric oxygen atom between carbon-carbon atoms. As (O) t -Q 5 From the viewpoint of ease of production of the compound (23), -CH is preferred 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 -or-CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 - (where the right side is bonded to Si).
As Q 6 The alkylene group having 1 to 10 carbon atoms or the group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms is preferable, and the single bond, the alkylene group having 1 to 7 carbon atoms or the group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group having 2 to 7 carbon atoms is particularly preferable. As Q 6 From the viewpoint of ease of production of compound (24), -CH is preferred 2 CH 2 CH 2 -or-CH 2 CH 2 OCH 2 CH 2 CH 2 - (where the right side is bonded to Si).
As Q 7 The alkylene group having 1 to 10 carbon atoms or the group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms is preferable, and the alkylene group having 1 to 7 carbon atoms or the group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group having 2 to 7 carbon atoms is particularly preferable. As Q 7 From the viewpoint of ease of production of compound (24), -CH is preferred 2 CH 2 CH 2 -or-CH 2 CH 2 OCH 2 CH 2 CH 2 - (wherein, the right side and SiR 3 n L 3-n Combined).
As Q 8 Preferably, the alkylene group has 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 to 10 carbon atoms. As Q 8 The alkylene group having 2 to 6 carbon atoms is preferable in view of easy production of the compound (25).
As Q 9 The alkylene group is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having 2 to 10 carbon atoms. As Q 9 From the viewpoint of ease of production of the compound (26), a single bond, -CH is preferred 2 -、-CH 2 CH 2 -。
As Q 10 Preferably, the alkylene group has 1 to 10 carbon atoms, or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 to 10 carbon atoms. As Q 10 From the viewpoint of ease of production of compound (26), -CH is preferred 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 -。
Q 11 The silylene skeleton in (A) is-Si (R) a ) 2 PhSi(R a ) 2 - (wherein Ph is phenylene, R) a Is a 1-valent organic group). R is a An alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is particularly preferable.
Q 11 The dialkylsilylene group in (1) is-Si (R) b ) 2 - (wherein, R) b Is alkyl). R is b An alkyl group having 1 to 10 carbon atoms is preferable, and a methyl group is particularly preferable.
As Q 11 Preferably C1-10 alkylene, or a group having an etheric oxygen atom or a silaphenylene skeleton between the C-C atoms of C2-10 alkyleneOr an organopolysiloxane residue having a valence of 2 or a dialkylsilylene group at the end on the carbon-carbon atom side of an alkylene group having 2 to 10 carbon atoms or on the side bonded to O. As Q 11 From the viewpoint of ease of production of the compound (27), -CH is preferred 2 CH 2 CH 2 -、-Si(CH 3 ) 2 CH 2 CH 2 CH 2 -、-Si(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 Si(CH 3 ) 2 PhSi(CH 3 ) 2 CH 2 CH 2 - (where the right side is bonded to Si).
As Q 12 The alkylene group having 1 to 10 carbon atoms or the alkylene group having 2 to 10 carbon atoms and having an etheric oxygen atom between carbon atoms is preferable. As Q 12 From the viewpoint of ease of production of the compound (27), -CH is preferred 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 - (where the right side is bonded to Si).
As Q 13 The alkylene group having 1 to 10 carbon atoms or the alkylene group having 2 to 10 carbon atoms and having an etheric oxygen atom between carbon atoms is preferable. As Q 13 From the viewpoint of ease of production of the compound (28), it is preferably-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 -、-CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 - (where the right side is bonded to Si).
(R 5 radical-R 6 Base)
As R 5 And R 6 Preferably a hydrogen atom. At R 5 Or R 6 In the case of an alkyl group, the carbon number is preferably 1 to 4.
(SiR 3 n L 3-n Base)
SiR 3 n L 3-n Is a hydrolyzable silyl group.
The surface treatment agent has a hydrolyzable silyl group at the end. The surface treatment agent having such a structure is strongly chemically bonded to the base material, and therefore, the surface layer is excellent in abrasion resistance.
The surface treatment agent has a hydrolyzable silyl group only at one end. The surface treatment agent having such a structure is less likely to aggregate, and therefore the surface layer has an excellent appearance.
L is a hydrolyzable group. The hydrolyzable group is a group that forms a hydroxyl group by a hydrolysis reaction. That is, si-L at the terminal of the surface treatment agent forms a silanol group (Si-OH) by hydrolysis reaction. Further reaction between silanol-based molecules forms Si-O-Si bonds. In addition, the silanol group and the hydroxyl group on the surface of the substrate (substrate-OH) undergo a dehydration condensation reaction to form a chemical bond (substrate-O-Si).
Examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The halogen atom is preferably a chlorine atom.
The L is preferably an alkoxy group or a halogen atom, from the viewpoint of ease of production of the surface treatment agent. The L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoints of less outgassing during application (Japanese: 1245054124881246073.
R 3 Is a hydrogen atom or a 1-valent hydrocarbon group. Examples of the hydrocarbyl group having a valence of 1 include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group.
As R 3 The hydrocarbon group having a valence of 1 is preferable, and the saturated hydrocarbon group having a valence of 1 is particularly preferable.
R 3 The number of carbon atoms in the 1-valent hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1 to 2.R 3 When the number of carbon atoms is in this range, the compound (5) can be easily produced.
n is preferably 0 or 1, particularly preferably 0. When a plurality of L groups are present in 1 hydrolyzable silyl group, adhesion to the substrate is further enhanced.
As SiR 3 n L 3-n Preferably Si (OCH) 3 ) 3 、SiCH 3 (OCH 3 ) 2 、Si(OCH 2 CH 3 ) 3 、SiCl 3 、Si(O(O)CCH 3 ) 3 、Si(NCO) 3 . Si (OCH) is particularly preferable from the viewpoint of ease of handling in industrial production 3 ) 3 。
From the viewpoint of ease of production of the surface treatment agent, siRs in the compounds (22) to (24) and (26) to (28) 3 n L 3-n Preferably the same group.
(specific examples of surface treatment agent)
Specific examples of the compound (21) include compounds of the following formula.
[ solution 4]
Specific examples of the compound (22) include compounds represented by the following formula.
[ solution 5]
Specific examples of the compound (23) include compounds represented by the following formula.
[ solution 6]
Specific examples of the compound (24) include compounds of the following formula.
[ solution 7]
Specific examples of the compound (25) include compounds represented by the following formula.
[ solution 8]
Specific examples of the compound (26) include compounds of the following formula.
[ solution 9]
Specific examples of the compound (27) include compounds represented by the following formula.
[ solution 10]
Specific examples of the compound (28) include compounds represented by the following formula.
[ solution 11]
Wherein PFPE is a polyfluoropolyether chain, i.e. F-R f2 O-(R f1 O) m -R f2 -. The preferred form of PFPE is as described above for (R) f1 O) m And R f2 The combination of the two components.
(method for producing surface treatment agent)
The compound (21) can be produced by a known method described in patent document 1, patent document 2, international publication No. 2013/121984, and the like.
Compound (22) can be produced by a known method described in international publication No. 2017/038832.
The compound (23) can be produced by a known method described in international publication No. 2017/038830.
Compound (24) can be produced by a known method described in Japanese patent laid-open publication No. 2016-037541, international publication No. 2016/121211, and the like.
The compound (25) can be produced by a known method described in international publication No. 2013/121984.
Compound (26) can be produced by a known method described in international publication No. 2017/038830.
Compound (27) can be produced by a known method described in Japanese patent laid-open No. 2016-204656.
Compound (28) can be produced by a known method described in JP 2016-037541A.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
Hereinafter, "%" represents "% by mass" unless otherwise specified.
Examples 1 to 4 are examples, and examples 5 to 6 are production examples.
[ example 1]
Example 1-1
Into a 200mL three-necked flask were charged 11.8g of ethanol and 100.0g of compound (1-1) (manufactured by Soviusulickss Co., ltd., FOMBLIN (registered trademark) ZDAC 4000), and the mixture was stirred at 50 ℃ for 4 hours. The reaction mixture was concentrated by an evaporator to obtain 100.4g of a crude product. The crude product was developed by silica gel column chromatography and separated. Using CF 3 CH 2 OCF 2 CF 2 H (AE-3000 manufactured by AGC Co., ltd.) was used as a developing solvent to elute the compound (3-1). Compound (2-1) was eluted using AE-3000/acetone =7/3 (mass ratio) as a developing solvent. Compound (1-1) was eluted using AE-3000/2,2, 2-trifluoroethanol =2/8 (mass ratio) as a developing solvent. For each component obtained, from 1 H-NMR and 19 the integral value of F-NMR was used to calculate the average of the structure of the terminal group and the number of units (x 1, x 2) of the structural unit. 24.1g of the reaction solution was obtainedCompound (1-1) (yield: 24.1%), 48.4g of compound (2-1) (yield: 48.1%), and 25.9g of compound (3-1) (yield: 25.6%).
HO(O)C-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OH…(1-1)
HO(O)C-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCH 2 CH 3 …(2-1)
CH 3 CH 2 O(O)C-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCH 2 CH 3 …(3-1)
NMR spectra of Compound (1-1):
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.1～-55.4(38F)、-77.8(2F)、-79.8(2F)、-89.2～-90.8(84F)
Average value of the number of cells x 1: average of cell number x 2: 21, number average molecular weight of Compound (1-1): 3900.
NMR spectrum of Compound (2-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: tetramethylsilane (TMS)) δ (ppm): 4.3 (2H) and 1.3 (3H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.2～-55.5(38F)、-77.8(1F)、-78.3(1F)、-79.9(2F)、-89.3～-90.9(84F)。
Average of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (2-1): 3920.
NMR spectrum of Compound (3-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 4.3 (4H), 1.3 (6H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.2～-55.5(38F)、-78.3(2F)、-80.0(2F)、-89.3～-90.9(84F)。
Average value of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (3-1): 3940.
(examples 1 and 2)
A cooler maintained at 20 ℃, a NaF particle packed layer, and a cooler maintained at 0 ℃ were provided in series at the gas outlet of a 500mL nickel autoclave. A liquid return line for returning the liquid condensed by the cooler maintained at 0 ℃ to the autoclave was provided.
350g of ClCF was charged into the autoclave 2 CFClCF 2 OCF 2 CF 2 Cl (CFE-419), with stirring, was maintained at 25 ℃. After nitrogen gas was blown into the autoclave at 25 ℃ for 1 hour, 20% fluorine gas was blown into the autoclave at 25 ℃ and a flow rate of 1.0L/hour for 1 hour. Next, while blowing 20% fluorine gas at the same flow rate, a solution obtained by dissolving 40.0g of the compound (2-1) obtained in example 1-1 in 120g of CFE-419 was injected into the autoclave over 4 hours. While blowing 20% fluorine gas at the same flow rate, the internal pressure of the autoclave was increased to 0.15MPa (gauge pressure). While 6mL of a benzene solution containing 0.05g/mL of benzene in CFE-419 was injected into the autoclave, the autoclave was heated from 25 ℃ to 40 ℃ and the inlet for the benzene solution in the autoclave was closed. After stirring for 15 minutes, 6mL of benzene solution was again injected while maintaining the temperature at 40 ℃ and the injection port was closed. The same operation was further repeated 3 times. The total amount of benzene injected was 1.5g. While blowing 20% fluorine gas at the same flow rate, stirring was continued for 1 hour. The pressure in the autoclave was set to atmospheric pressure, and nitrogen gas was blown into the autoclave for 1 hour. The contents of the autoclave were concentrated by an evaporator to obtain 39.8g of compound (4-1) (yield 97.9%).
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCF 2 CF 3 …(4-1)
NMR spectrum of Compound (4-1):
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(38F)、-56.3～-58.3(3F)、-77.8(1F)、-78.3(1F)、-87.5(3F)、-89.0～-90.9(86F)。
Average value of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (4-1): 3980.
examples 1 to 3
39.0g of the compound (4-1) obtained in example 1-2 and 50g of AE-3000 were placed in a round-bottomed flask made of tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer (PFA). While stirring the mixture with cooling in an ice bath, 3.2g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere. Stirring was carried out for 12 hours while bubbling nitrogen gas. The reaction mixture was concentrated by an evaporator to obtain 37.7g of compound (5-1) (yield 99.4%).
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCH 3 …(5-1)
NMR spectrum of Compound (5-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 3.9 (3H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(38F)、-56.3～-58.3(3F)、-78.2(1F)、-79.9(1F)、-89.0～-90.9(84F)。
Average of the number of cells x 1: average of cell number x 2: 21, number average molecular weight of Compound (5-1): 3880.
examples 1 to 4
In a 200mL three-necked flask, 1.80g of sodium borohydride was dissolved in 10g of ethanol and 20g of AE-3000, and a solution obtained by mixing 37.0g of the compound (5-1) obtained in example 1-3 and 37.0g of AE-3000 was slowly added dropwise while cooling with an ice bath. The ice bath was removed and stirring was continued while slowly warming to room temperature. After stirring at room temperature for 12 hours, an aqueous hydrochloric acid solution was added dropwise until the pH value became acidic. The organic phase was collected, washed with water for 1 time and saturated brine for 1 time, and the organic phase was recovered. The recovered organic phase was concentrated by an evaporator to obtain 36.5g of compound (6-1) (yield 98.2%).
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -CH 2 OH…(6-1)
NMR spectrum of Compound (6-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 3.9 (2H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(38F)、-56.3～-58.3(3F)、-80.7(1F)、-82.8(1F)、-89.0～-90.9(84F)。
Average of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (6-1): 3900.
[ example 2]
Into a 100mL eggplant-shaped flask were charged 25.0g of the compound (3-1) obtained in example 1-1 and 2.0g of a 48% aqueous solution of sodium hydroxide, and the mixture was stirred at 80 ℃ for 2 hours. The mixture was transferred to a separatory funnel, 30mL of dilute hydrochloric acid was added, and 30mL of AE-3000 was used for extraction 5 times. The recovered solution was concentrated by an evaporator to obtain 22.6g of compound (1-1) (yield 97.1%).
Compound (6-1) was obtained in the same manner as in example 1, except that 22.6g of Compound (1-1) regenerated from Compound (3-1) was used and the amount of each raw material was changed to suit the amount of Compound (1-1).
The compound (3-1) can be reused as the compound (1-1), and it can be said that there is almost no waste of the fluorine-containing ether compound by reusing the compound (3-1).
[ example 3]
(example 3-1)
A100 mL three-necked flask was charged with 20.0g of the compound (1-1) and 20.0g of the compound (6-1) obtained in example 1-4, and the mixture was stirred while being heated to 80 ℃. Water produced as a by-product was distilled off under reduced pressure, and the disappearance of compound (6-1) was confirmed by NMR analysis. The obtained crude product was purified in the same manner as in example 1-1 to obtain 5.2g of compound (1-1) (yield: 25.8%), 19.1g of compound (12-1) (yield: 48.0%) and 14.5g of compound (13-1) (yield: 24.2%).
HO(O)C-CF 2 -O{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OH…(1-1)
HO(O)C-CF 2 -O{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCH 2 -CF 2 -{(OCF 2 CF 2 ) x2 (OCF 2 ) x1 }-OCF 2 -F…(12-1)
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -CH 2 O(O)C-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCH 2 -CF 2 -{(OCF 2 CF 2 ) x2 (OCF 2 ) x1 }-OCF 2 -F…(13-1)
NMR spectra of Compound (1-1):
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.1～-55.4(38F)、-77.8(2F)、-79.8(2F)、-89.2～-90.8(84F)。
Average of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (1-1): 3900.
NMR spectrum of Compound (12-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 4.8 (2H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.2～-55.5(76F)、-56.3～-58.3(3F)、-77.0～-80.3(6F)、-89.3～-90.9(168F)。
Average value of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (12-1): 7730.
NMR spectrum of Compound (13-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 4.8 And (4H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.2～-55.5(114F)、-56.3～-58.3(6F)、-77.5～-80.3(8F)、-89.3～-90.9(252F)。
Average value of the number of cells x 1: average of cell number x 2: 21, number average molecular weight of Compound (13-1): 11570.
(example 3-2)
18.8g of compound (14-1) was obtained in the same manner as in example 1-2, except that the amount of compound (2-1) was changed to 19.0g of compound (12-1) and the amounts of the respective starting materials were changed in accordance with the amount of compound (12-1) (yield 98.8%).
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCF 2 -CF 2 -{(OCF 2 CF 2 ) x2 (OCF 2 ) x1 }-OCF 2 -F…(14-1)
NMR spectrum of Compound (14-1):
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(76F)、-56.3～-58.3(6F)、-77.8(1F)、-78.3(1F)、-89.0～-90.9(172F)。
Average of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (14-1): 7740.
(examples 3 to 3)
18.2g of compound (5-1) was obtained in the same manner as in example 1-3, except that the amount of compound (4-1) was changed to 18.5g of compound (14-1) and the amounts of the respective starting materials were changed in accordance with the amount of compound (14-1) (yield 96%).
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)OCH 3 …(5-1)
NMR spectrum of Compound (5-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 3.9 (3H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(38F)、-56.3～-58.3(3F)、-78.2(1F)、-79.9(1F)、-89.0～-90.9(84F)。
Average of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (5-1): 3880.
the compound (5-1) can be derived as the compound (6-1) in the same manner as in example 1-4, similarly to the compound (5-1) obtained in example 1.
[ example 4]
Into a 50mL eggplant type flask were charged 14.0g of the compound (13-1) obtained in example 3-1 and 1.0g of a 48% aqueous solution of sodium hydroxide, and the mixture was stirred at 80 ℃ for 2 hours. This was transferred to a separatory funnel, 20mL of dilute hydrochloric acid was added, and extraction was performed 5 times with 20mL of AE-3000. The recovered solution was concentrated by an evaporator, and the obtained crude liquid was purified by silica gel column chromatography to obtain 4.4g of compound (1-1) (yield 93.3%) and 9.2g of compound (6-1) (yield 197%).
The compound (13-1) can be reused as the compound (1-1) and the compound (6-1), and it can be said that there is almost no waste of the fluorine-containing ether compound by reusing the compound (13-1).
[ example 5]
Production example of surface treatment agent Using Compound (5-1)
According to the methods described in examples 1 to 6 of international publication No. 2013/121984, a surface treatment agent was produced. It was confirmed by NMR that 99% of the compound (5-1) was converted into the compound (25-1).
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -C(O)NH-CH 2 CH 2 CH 2 -Si(OCH 3 ) 3 …(25-1)
NMR spectrum of Compound (25-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 0.6 (2H), 1.6 (2H), 2.8 (1H), 3.2 (2H), 3.5 (9H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(38F)、-56.3～-58.3(3F)、-81.3(1F)、-84.1(1F)、-89.0～-90.9(84F)。
Average of the number of cells x 1: 19, average of cell number x 2: 21, number average molecular weight of Compound (25-1): 4050.
[ example 6]
(example of production of surface treating agent Using Compound (6-1))
Compound (23-1) was obtained according to the method described in example 4 of International publication No. 2017/038830.
F-CF 2 O-{(CF 2 O) x1 (CF 2 CF 2 O) x2 }-CF 2 -CH 2 O-CH 2 -C[-CH 2 CH 2 CH 2 -Si(OCH 3 ) 3 ] 3 …(23-1)
NMR spectrum of Compound (23-1):
1 H-NMR (300.4 MHz, solvent: CDCl) 3 And standard: TMS) δ (ppm): 0.7 (6H), 1.7 (6H), and 3.4-3.8 (37H).
19 F-NMR (282.7 MHz, solvent: CDCl) 3 And standard: CFCl 3 )δ(ppm)：-52.3～-55.6(38F)、-56.3～-58.3(3F)、-77.3(1F)、-79.3(1F)、-89.0～-90.9(84F)。
Average value of the number of cells x 1: average of cell number x 2: 21, number average molecular weight of Compound (23-1): 4370.
possibility of industrial utilization
The fluorine-containing ether compound obtained by the production method of the present invention can be used in various applications requiring lubricity imparting and water and oil repellency imparting. For example, it can be used for a display input device such as a touch panel; a surface protective coating for a transparent glass or transparent plastic member, and an antifouling coating for kitchens; water-repellent moisture-proof coatings and antifouling coatings for electronic devices, heat exchangers, batteries, and the like, antifouling coatings for cosmetics; coatings on components that are electrically conductive and require liquid repellency; water repellent, water resistant and water slippery coatings for heat exchangers; low friction coatings on the surfaces of the shaker screen and the piston interior, etc. More specific examples of the use thereof include front surface protective plates for displays, antireflection plates, polarizing plates, antiglare plates, articles having antireflection film-treated surfaces thereof, various devices having display input devices for performing image operations on human fingers or palms such as touch panels or touch panels of devices such as mobile phones and portable information terminals, decorative building materials around water in toilets, bathrooms, kitchens, etc., waterproof coatings for wiring boards, water-repellent waterproof coatings for heat exchangers, water-repellent coatings for solar cells, water-repellent coatings for printed circuit boards, water-repellent waterproof coatings for electronic device housings and electronic parts, insulating property-improving coatings for power transmission lines, waterproof and water-repellent coatings for various filters, water-repellent coatings for electromagnetic wave absorbing materials and sound absorbing materials, water-repellent coatings for bathrooms, kitchen devices, antifouling coatings for cosmetics, water-repellent and water-repellent coatings for heat exchangers, water-repellent and water-repellent coatings, surface low-friction coatings for vibration sieves, piston interiors and the like, mechanical devices, vacuum device parts, bearing parts, automobile parts, tools, and surface protective coatings for tools.
The entire contents of the specification, claims and abstract of japanese patent application No. 2017-104614 filed on 2017, 5, 26 are cited herein as disclosure of the specification of the present invention.
Claims (6)
1. A process for producing a fluorine-containing ether compound, which comprises reacting R with an alcohol 1 A method for obtaining a mixture comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3) by reacting OH with the compound represented by the following formula (1), wherein the compound represented by the formula (3) is recovered and hydrolyzed to obtain the compound represented by the formula (1) as the compound represented by the formula (1) and the R 1 The compound represented by the formula (1) in the reaction of OH is reused,
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(2)
R 1 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(3)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 1 is a 1-valent hydrocarbon group which may contain an etheric oxygen atom or a hydrogen atom, a part of which may be substituted with a fluorine atom.
2. A process for producing a fluorine-containing ether compound, which comprises reacting R 1 A method for reacting OH with a compound represented by the following formula (1) to obtain a mixture comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3),
recovering the unreacted compound represented by the formula (1) as the compound represented by the formula (1) and the R 1 The compound represented by the formula (1) in the reaction of OH is reused,
and recovering the compound represented by the formula (3), and hydrolyzing to obtain the compound represented by the formula (1) as the compound represented by the formula (1) and the compound represented by the formula R 1 The compound represented by the formula (1) in the reaction of OH is reused,
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OH…(1)
HO(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(2)
R 1 O(O)C-R f2 O-(R f1 O) m -R f2 -C(O)OR 1 …(3)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 1 is a compound having a valence of 1 which may contain an etheric oxygen atom or a hydrogen atom, a part of which may be substituted with a fluorine atomA hydrocarbon group of (1).
3. The method for producing a fluorinated ether compound according to claim 1 or 2, wherein R is the number 1 OH, a compound represented by the following formula (6) is used,
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is each independently an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 And O.
4. A process for producing a fluorine-containing ether compound, characterized by obtaining the mixture by the production process according to any one of claims 1 to 3, recovering the compound represented by the formula (2) from the mixture, fluorinating the compound represented by the formula (2) with a fluorine gas to obtain a compound represented by the following formula (4),
F-R f2 O-(R f1 O) m -R f2 -C(O)OR f3 …(4)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R f3 is derived from R 1 A 1-valent perfluoroorganic group of (1).
5. A method for producing a fluorine-containing ether compound, characterized in that the compound represented by the formula (4) is obtained by the production method of claim 4, and the compound represented by the formula (4) and R are reacted 2 Performing ester exchange on OH to obtain a compound shown in a following formula (5),
F-R f2 O-(R f1 O) m -R f2 -C(O)OR 2 …(5)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 O, and the mixture is mixed to form the alloy,
R 2 is a hydrocarbyl radical having a valence of 1.
6. A method for producing a fluorine-containing ether compound, characterized in that the compound represented by the formula (5) is obtained by the production method according to claim 5, the compound represented by the formula (5) is reduced by hydrogenation using a reducing agent, and a compound represented by the following formula (6) is obtained,
F-R f2 O-(R f1 O) m -R f2 -CH 2 OH…(6)
wherein,
R f1 and R f2 Each of which is independently a perfluoroalkylene group,
m is an integer of 2 to 200,
(R f1 O) m can be composed of more than 2 kinds of R f1 And O.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847978A (en) * | 1968-07-01 | 1974-11-12 | Montedison Spa | Perfluorinated linear polyethers having reactive terminal groups at both ends of the chain and process for the preparation thereof |
| US5132455A (en) * | 1982-03-31 | 1992-07-21 | Exfluor Research Corporation | Method for synthesizing perfluorinated ether compounds via polyesters |
| JPH09136952A (en) * | 1995-11-16 | 1997-05-27 | Hitachi Ltd | Fluorine compound, surface modifier and magnetic disc device using the same |
| CN104114566A (en) * | 2012-02-17 | 2014-10-22 | 旭硝子株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition and coating fluid, and substrate having surface-treated layer and method for producing said substrate |
| CN105492418A (en) * | 2013-08-26 | 2016-04-13 | 旭硝子株式会社 | Method for producing fluorinated compound |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847978A (en) * | 1968-07-01 | 1974-11-12 | Montedison Spa | Perfluorinated linear polyethers having reactive terminal groups at both ends of the chain and process for the preparation thereof |
| US5132455A (en) * | 1982-03-31 | 1992-07-21 | Exfluor Research Corporation | Method for synthesizing perfluorinated ether compounds via polyesters |
| JPH09136952A (en) * | 1995-11-16 | 1997-05-27 | Hitachi Ltd | Fluorine compound, surface modifier and magnetic disc device using the same |
| CN104114566A (en) * | 2012-02-17 | 2014-10-22 | 旭硝子株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition and coating fluid, and substrate having surface-treated layer and method for producing said substrate |
| CN105492418A (en) * | 2013-08-26 | 2016-04-13 | 旭硝子株式会社 | Method for producing fluorinated compound |
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